阅读说明：本技术 一种高性能铜合金及其制备方法 (High-performance copper alloy and preparation method thereof ) 是由 接金川 李廷举 王同敏 张宇博 卢一平 曹志强 康慧君 陈宗宁 郭恩宇 于 2021-09-07 设计创作，主要内容包括：本发明提供了一种高性能铜合金及其制备方法,属于金属材料制备领域。本发明提供的高性能铜合金通过添加Zn可使铜基体获得与黄铜相近的性能,同时通过添加Ni和Si作为强化元素,可以在铜基体中形成析出相颗粒,从而有效强化铜合金的力学性能并保证铜合金具有较高的导电性；并且本发明通过控制Fe和Pb的含量能够尽可能降低其对铜合金的不利影响,从而有效保证其他强化元素对铜合金性能的提高。实施例的结果表明,本发明制备的铜合金的抗拉强度可以达到586～707MPa,屈服强度可以达到479～604MPa,导电率可以达到21～24％IACS。(The invention provides a high-performance copper alloy and a preparation method thereof, belonging to the field of metal material preparation. According to the high-performance copper alloy provided by the invention, the performance of a copper matrix can be similar to that of brass by adding Zn, and precipitated phase particles can be formed in the copper matrix by adding Ni and Si as reinforcing elements, so that the mechanical property of the copper alloy is effectively reinforced and the copper alloy is ensured to have higher conductivity; in addition, the adverse effect of Fe and Pb on the copper alloy can be reduced as much as possible by controlling the contents of Fe and Pb, so that the improvement of the performance of the copper alloy by other strengthening elements is effectively ensured. The results of the embodiment show that the tensile strength of the copper alloy prepared by the invention can reach 586-707 MPa, the yield strength can reach 479-604 MPa, and the electric conductivity can reach 21-24% IACS.)

1. A high-performance copper alloy comprises the following components in percentage by mass: zn27.32-29.9%, Ni0.06-1.5%, Si0.01-0.3%, Fe < 0.1%, Pb < 0.08% and the balance of Cu;

the mass ratio of the Ni to the Si is (4-6): 1.

2. the high performance copper alloy of claim 1, comprising the following components in mass percent: zn27.5-29.3%, Ni0.08-1.4%, Si0.02-0.25%, Fe < 0.08%, Pb < 0.06% and the balance of Cu; the mass ratio of the Ni to the Si is (4.2-5.8): 1.

3. the high performance copper alloy of claim 2, comprising the following components in mass percent: zn28.0-29.0%, Ni0.1-1.3%, Si0.03-0.2%, Fe < 0.05%, Pb < 0.05% and the balance of Cu; the mass ratio of the Ni to the Si is (4.3-5.7): 1.

4. the high performance copper alloy of claim 3, comprising the following components in mass percent: zn28.3-28.8%, Ni0.2-1.1%, Si0.04-0.15%, Fe < 0.03%, Pb < 0.03% and the balance of Cu; the mass ratio of the Ni to the Si is (4.5-5.5): 1.

5. the method for preparing the high-performance copper alloy according to any one of claims 1 to 4, comprising the steps of:

(1) smelting and casting alloy raw materials in sequence to obtain a casting material;

(2) and (2) sequentially carrying out rolling, annealing treatment, solid solution treatment and aging treatment on the cast material obtained in the step (1) to obtain the high-performance copper alloy.

6. The preparation method of claim 5, wherein the temperature of the smelting in the step (1) is 1100-1200 ℃, and the time of the smelting is 7-15 min.

7. The preparation method of claim 5, wherein the rolling temperature in the step (2) is 720-880 ℃, the number of rolling passes is 7-14, the single-pass deformation of the rolling is 4-10%, and the total deformation of the rolling is 50-90%.

8. The method according to claim 5, wherein the annealing temperature in the step (2) is 200 to 400 ℃ and the annealing time is 30 to 150 min.

9. The method according to claim 5, wherein the temperature of the solution treatment in the step (2) is 620 to 780 ℃ and the time of the solution treatment is 510 to 690 min.

10. The method according to claim 5, wherein the temperature of the aging treatment in the step (2) is 370 to 430 ℃ and the time of the aging treatment is 150 to 210 min.

Technical Field

The invention relates to the field of metal material preparation, in particular to a high-performance copper alloy and a preparation method thereof.

Background

Brass is one of the most important copper alloy varieties, has high mechanical properties, has the inherent characteristics of electric conduction, heat conduction, easy processing and the like of copper alloy, is relatively cheap and low in production cost, so that the copper alloy with the largest use amount in various fields in China is widely used for heat exchangers, valves, drainage pipelines, radiators, important parts in ships, chemical machinery and electrical instruments, connectors and fittings of electronic and telecommunication equipment and household appliances, interior decoration, clothing ornaments, water tanks for vehicles, batteries and the like.

Among them, H65 brass is one of the most representative ones. However, with the rapid development of the electronic, electrical and power industries, the demand of brass with both excellent mechanical properties and electrical conductivity has increased greatly year by year. Therefore, the existing H65 brass in China cannot meet the higher use requirement of the connector in the field of electric power and electric appliances in the aspects of high strength, high plasticity and good conductivity. The H65 brass is a solid solution alloy, wherein the zinc element is formed as an alpha solid solution alloy of solid solution atoms and a copper matrix, the H65 brass is adversely affected by reducing or increasing the zinc element, and a precipitated phase is easily formed by adding other alloy elements, so that the brittleness and the mechanical property of the H65 brass are increased, and the electrical conductivity of the H65 brass is greatly reduced.

Therefore, how to balance the mechanical property and the electrical conductivity of the brass to obtain high-performance brass with excellent comprehensive performance becomes a difficult problem to be solved in the prior art.

Disclosure of Invention

The invention aims to provide a high-performance copper alloy and a preparation method thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a high-performance copper alloy which comprises the following components in percentage by mass: 27.32-29.9% of Zn, 0.06-1.5% of Ni, 0.01-0.3% of Si, 0.1% of Fe, 0.08% of Pb and the balance of Cu;

the mass ratio of the Ni to the Si is (4-6): 1.

preferably, the high-performance copper alloy comprises the following components in percentage by mass: 27.5-29.3% of Zn, 0.08-1.4% of Ni, 0.02-0.25% of Si, 0.08% of Fe, 0.06% of Pb and the balance of Cu; the mass ratio of the Ni to the Si is (4.2-5.8): 1.

preferably, the high-performance copper alloy comprises the following components in percentage by mass: 28.0-29.0% of Zn, 0.1-1.3% of Ni, 0.03-0.2% of Si, 0.05% of Fe, 0.05% of Pb and the balance of Cu; the mass ratio of the Ni to the Si is (4.3-5.7): 1.

preferably, the high-performance copper alloy comprises the following components in percentage by mass: 28.3-28.8% of Zn, 0.2-1.1% of Ni, 0.04-0.15% of Si, 0.03% of Fe, 0.03% of Pb and the balance of Cu; the mass ratio of the Ni to the Si is (4.5-5.5): 1.

the invention also provides a preparation method of the high-performance copper alloy, which comprises the following steps:

(1) smelting and casting alloy raw materials in sequence to obtain a casting material;

(2) and (2) sequentially carrying out rolling, annealing treatment, solid solution treatment and aging treatment on the cast material obtained in the step (1) to obtain the high-performance copper alloy.

Preferably, the heat preservation temperature of the smelting in the step (1) is 1100-1200 ℃, and the heat preservation time of the smelting is 7-15 min.

Preferably, the rolling temperature in the step (2) is 720-880 ℃, the rolling passes are 7-14, the single-pass deformation amount of the rolling is 4-10%, and the total deformation amount of the rolling is 50-90%.

Preferably, the temperature of the annealing treatment in the step (2) is 200-400 ℃, and the time of the annealing treatment is 30-150 min.

Preferably, the temperature of the solution treatment in the step (2) is 620-780 ℃, and the time of the solution treatment is 510-690 min.

Preferably, the temperature of the aging treatment in the step (2) is 370-430 ℃, and the time of the aging treatment is 150-210 min.

The invention provides a high-performance copper alloy which comprises the following components in percentage by mass: 27.32-29.9% of Zn, 0.06-1.5% of Ni, 0.01-0.3% of Si, 0.1% of Fe, 0.08% of Pb and the balance of Cu; the mass ratio of the Ni to the Si is (4-6): 1. according to the invention, Zn is added to enable the copper matrix to obtain the performance similar to that of brass, and meanwhile, Ni and Si are added as strengthening elements to form precipitated phase particles in the copper matrix, so that the mechanical property of the copper alloy is effectively strengthened and the copper alloy is ensured to have higher conductivity; in addition, the adverse effect of Fe and Pb on the copper alloy can be reduced as much as possible by controlling the contents of Fe and Pb, so that the improvement of the performance of the copper alloy by other strengthening elements is effectively ensured. The results of the embodiment show that the tensile strength of the copper alloy prepared by the invention can reach 586-707 MPa, the yield strength can reach 479-604 MPa, and the electric conductivity can reach 21-24% IACS.

Detailed Description

The invention provides a high-performance copper alloy which comprises the following components in percentage by mass: 27.32-29.9% of Zn, 0.06-1.5% of Ni, 0.01-0.3% of Si, 0.1% of Fe, 0.08% of Pb and the balance of Cu;

the mass ratio of the Ni to the Si is (4-6): 1.

according to the mass percentage, the high-performance copper alloy provided by the invention comprises 27.32-29.9% of Zn, preferably 27.5-29.3%, more preferably 28.0-29.0%, and most preferably 28.3-28.8%. According to the invention, the performance of the copper matrix is similar to that of brass by adding Zn, and meanwhile, the Zn content is controlled within the range, so that the copper matrix has good plasticity, and the brittleness of the copper matrix is reduced, thereby being more beneficial to improving the mechanical property of the copper matrix through plastic deformation such as rolling and the like and being not easy to crack.

According to the mass percentage, the high-performance copper alloy provided by the invention comprises 0.06-1.5% of Ni, preferably 0.08-1.4%, more preferably 0.1-1.3%, and most preferably 0.2-1.1%. According to the invention, by adding Ni element and controlling the content of the Ni element within the range, part of Ni can be dissolved in the copper matrix in a solid mode, and meanwhile, part of Ni can be combined with other alloying elements to form fine and uniformly distributed precipitated phase particles in the copper-nickel-tin alloy, so that the mechanical property of the copper alloy is effectively enhanced.

According to the mass percentage, the high-performance copper alloy provided by the invention comprises 0.01-0.3% of Si, preferably 0.02-0.25%, more preferably 0.03-0.2%, and most preferably 0.04-0.15%. According to the invention, by adding the Si element and controlling the content of the Si element within the range, the Si element and the Ni can be combined to form precipitated phase particles, so that the mechanical property of the copper alloy is effectively enhanced and the copper alloy is ensured to have higher conductivity.

In the invention, the mass ratio of Ni to Si is (4-6): 1, preferably (4.2-5.8): 1, more preferably (4.3 to 5.7): 1, most preferably (4.5-5.5): 1. by controlling the addition ratio of Ni and Si within the range, the intermetallic compound of Ni and Si can be formed in the copper matrix and uniformly precipitated in the copper matrix in a precipitated phase form, so that the mechanical property of the copper alloy is effectively enhanced and the high conductivity of the copper alloy is ensured.

The high performance copper alloy provided by the present invention comprises, in mass percent, < 0.1% Fe, preferably < 0.06%, more preferably < 0.05%, most preferably < 0.03%. In the present invention, the Fe is present as an impurity in the high performance copper alloy. According to the invention, the content of Fe is controlled within the range, so that the adverse effect of Fe on the copper alloy can be reduced as much as possible, and the improvement of other strengthening elements on the performance of the copper alloy is effectively ensured.

The high performance copper alloy provided by the present invention comprises < 0.08% Pb, preferably < 0.08%, more preferably < 0.05%, most preferably < 0.03% by mass. In the present invention, the Pb is present as an impurity in the high performance copper alloy. By controlling the content of Pb within the range, the adverse effect of Pb on the copper alloy can be reduced as much as possible, so that the improvement of the performance of the copper alloy by other strengthening elements is effectively ensured.

According to the mass percentage, the high-performance copper alloy provided by the invention comprises the balance of copper. According to the invention, copper is taken as a matrix, Zn, Ni and Si strengthening elements are added, and the contents of Fe and Pb are controlled, so that the strength and the conductivity of the copper matrix can be effectively improved.

The high-performance copper alloy provided by the invention can effectively improve the strength and the conductivity of a copper matrix by adding Zn, Ni and Si strengthening elements, controlling the addition ratio of Ni and Si and controlling the contents of Fe and Pb.

The invention also provides a preparation method of the high-performance copper alloy, which comprises the following steps:

(1) smelting and casting alloy raw materials in sequence to obtain a casting material;

(2) and (2) sequentially carrying out rolling, annealing treatment, solid solution treatment and aging treatment on the cast material obtained in the step (1) to obtain the high-performance copper alloy.

The invention carries out smelting and casting on alloy raw materials in sequence to obtain a casting material.

In the present invention, the alloy raw material is preferably electrolytic copper, pure zinc, pure nickel and pure silicon. In the invention, the purities of the electrolytic copper, the pure zinc, the pure nickel and the pure silicon are preferably more than or equal to 99.99%.

In the invention, the smelting temperature is preferably 1500-1600 ℃, and more preferably 1550-1600 ℃. The invention is more beneficial to the rapid melting of all raw materials to form a melt by smelting at a higher temperature, and avoids the problems of oxidation burning loss and the like caused by long-time semi-melting state of all raw materials.

In the invention, the heat preservation temperature of the smelting is preferably 1100-1200 ℃, more preferably 1130-1180 ℃, and most preferably 1150-1160 ℃; the heat preservation time of the smelting is preferably 7-15 min, more preferably 9-13 min, and most preferably 10-12 min. The invention can fully and uniformly diffuse each alloy element in the melt by keeping the temperature at the lower temperature than the melting temperature and controlling the temperature and the time in the above range, thereby being more beneficial to reducing element segregation and obtaining casting materials with uniform components.

In the present invention, the casting method is preferably horizontal continuous casting, semi-continuous casting or die casting, more preferably die casting.

After the cast material is obtained, the high-performance copper alloy is obtained by sequentially carrying out rolling, annealing treatment, solid solution treatment and aging treatment on the cast material.

In the invention, the rolling temperature is preferably 720-880 ℃, and more preferably 780-820 ℃; the rolling passes are preferably 7-14 times, and more preferably 9-12 times; the single-pass deformation of the rolling is preferably 4-10%, and more preferably 6-8%; the total deformation amount of the rolling is preferably 50-90%, and more preferably 65-75%. According to the invention, by controlling the rolling temperature, the rolling pass, the single-pass deformation and the total deformation, the casting defects such as shrinkage porosity and shrinkage cavity in the cast material can be effectively closed, and the conductivity of the copper alloy is effectively improved; meanwhile, more dislocation is obtained in the cast material structure through rolling deformation, crystal grains are refined, the problem that the copper alloy is easy to coarsen through subsequent continuous heat treatment is avoided, and therefore the mechanical property of the copper alloy is effectively improved.

In the invention, the annealing treatment temperature is preferably 200-400 ℃, more preferably 230-360 ℃, and most preferably 280-320 ℃; the time of the annealing treatment is preferably 30 to 150min, more preferably 40 to 120min, and most preferably 60 to 100 min. According to the invention, through annealing treatment and controlling the temperature and time within the range, the structural stress during rolling deformation can be effectively eliminated, the size of the copper alloy is stabilized, the structure is more uniform, and the mechanical property of the copper alloy is improved.

In the present invention, the cooling method of the annealing treatment is preferably air cooling.

In the invention, the temperature of the solution treatment is preferably 620-780 ℃, and more preferably 680-720 ℃; the time of the solution treatment is preferably 510-690 min, and more preferably 570-630 min. According to the invention, through solution treatment and temperature control within the range, all strengthening elements can be fully dissolved in the copper matrix in a solid manner, so that a uniform supersaturated solid solution structure is formed, and the subsequent aging treatment is more favorable for precipitating fine precipitated phases, so that the strength of the copper alloy is enhanced and the copper alloy has higher conductivity.

In the present invention, the solution treatment is preferably performed by water cooling.

In the invention, the temperature of the aging treatment is preferably 370-430 ℃, and more preferably 390-410 ℃; the time of the aging treatment is preferably 150-210 min, and more preferably 170-190 min. According to the invention, through aging treatment and controlling the temperature and time within the range, the strengthening elements in the supersaturated solid solution can form fine and uniformly distributed precipitated phase particles, so that the strength of the copper alloy is effectively enhanced and the copper alloy has high conductivity.

In the present invention, the cooling method of the aging treatment is preferably air cooling.

According to the preparation method of the high-performance copper alloy, uniform and fine precipitated phase particles are more favorably precipitated through a heat treatment mode of rolling, annealing, solid solution and aging after smelting and casting, so that the mechanical property of the copper alloy is effectively enhanced, and the copper alloy has high conductivity; meanwhile, the preparation method is simple and easy to control, safe, effective and low in cost.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The high-performance copper alloy prepared in the embodiment comprises the following components in percentage by mass: 27.8% of Zn, 0.52% of Ni, 0.01% of Si, 0.05% of Fe, 0.05% of Pb and the balance of Cu; the mass ratio of Ni to Si is 4.7: 1.

the preparation method of the high-performance copper-nickel-tin alloy comprises the following steps:

(1) adding alloy raw materials of electrolytic copper, pure nickel and pure silicon with the purity of more than or equal to 99.99 percent, and smelting and casting in sequence to obtain a casting material; wherein the smelting temperature is 1600 ℃, the heat preservation temperature is 1150 ℃, the heat preservation time is 13min, and the casting adopts horizontal continuous casting.

(2) Rolling the cast ingot obtained in the step (1) at 790 ℃ in sequence, wherein the rolling pass is 10, the single-pass deformation is 7%, and the total deformation is 70%; and after rolling, carrying out homogenizing annealing at 310 ℃ for 90min, cooling at room temperature, carrying out solution treatment at 710 ℃ for 570min, cooling with water, carrying out aging treatment at 410 ℃ for 210min, and cooling at room temperature to obtain the high-performance copper alloy.

Example 2

The high-performance copper alloy prepared in the embodiment comprises the following components in percentage by mass: 28.4% of Zn, 0.8% of Ni, 0.16% of Si, 0.05% of Fe, 0.04% of Pb and the balance of Cu; the mass ratio of Ni to Si is 5.0: 1.

the preparation method of the high-performance copper-nickel-tin alloy comprises the following steps:

(1) sequentially adding alloy raw materials of electrolytic copper, pure nickel and pure silicon with the purity of more than or equal to 99.99 percent, and sequentially smelting and casting to obtain a casting material; wherein the smelting temperature is 1600 ℃, the heat preservation temperature is 1160 ℃, the heat preservation time is 11min, and the casting adopts semi-continuous casting.

(2) Rolling the ingot obtained in the step (1) at 820 ℃ in sequence, wherein the rolling pass is 8, the single-pass deformation is 10%, and the total deformation is 80%; and after rolling, carrying out homogenizing annealing at 310 ℃ for 70min, cooling at room temperature, carrying out solution treatment at 710 ℃ for 630min, cooling with water, carrying out aging treatment at 390 ℃ for 170min, and cooling at room temperature to obtain the high-performance copper alloy.

Example 3

The high-performance copper alloy prepared in the embodiment comprises the following components in percentage by mass: 28.7% of Zn, 1.3% of Ni, 0.3% of Si, 0.04% of Fe, 0.04% of Pb and the balance of Cu; the mass ratio of Ni to Si is 4.3: 1.

the preparation method of the high-performance copper-nickel-tin alloy comprises the following steps:

(1) sequentially adding alloy raw materials of electrolytic copper, pure nickel and pure silicon with the purity of more than or equal to 99.99 percent, and sequentially smelting and casting to obtain a casting material; wherein the smelting temperature is 1600 ℃, the heat preservation temperature is 1160 ℃, the heat preservation time is 11min, and the casting adopts die casting.

(2) Rolling the cast ingot obtained in the step (1) at 800 ℃ in sequence, wherein the rolling pass is 10, the single-pass deformation is 7%, and the total deformation is 70%; and after rolling, carrying out homogenizing annealing at 300 ℃ for 60min, cooling at room temperature, carrying out solution treatment at 700 ℃ for 600min, cooling with water, carrying out aging treatment at 400 ℃ for 120min, and cooling at room temperature to obtain the high-performance copper alloy.

Comparative example 1

Commercially available conventional H65 brass was used as the copper alloy sample of comparative example 1.

Performance detection

The yield strength and the tensile strength of the copper alloy prepared in the examples 1-3 and the comparative example 1 are detected, the GB/T228.1-2010 metal material tensile test is adopted as the detection standard, and the detection results are shown in Table 1.

The conductivity of the copper alloy prepared in the examples 1-3 and the comparative example 1 was measured, the test standard adopted GB T11007-2008 conductivity meter test method, and the test results are shown in Table 1.

Table 1 test results of yield strength, tensile strength and electric conductivity of copper alloys prepared in examples 1 to 3 and comparative example 1

According to the table 1, the copper alloy prepared by the invention can effectively improve the yield strength and the tensile strength without causing the conductivity to be obviously reduced, so that the mechanical property of the copper nickel tin alloy can be effectively improved while the copper nickel tin alloy meets the use requirement of the conductivity.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.